Patent GB-701203-A (GB)
Title: New polyalkylidenes and their manufacture
IPC: C08G61/04
Filed: 1949-10-13
Abstract: Polyalkylidenes or interpolyalkylidenes are prepared by contacting a 1-diazoalkane containing 2 or 3 carbon atoms, or a mixture of a 1-diazoalkane of not more than 3 carbon atoms and a 1-diazoalkane of 2 or more carbon atoms, with copper or a copper-containing substance, and allowing the evolution of nitrogen.  The polyalkylidenes, which are glassy, have the formula -(R-CH)n, and the interpolyalkylidenes, which may be glassy or liquid, have the formula - (R. CH)a - (R1. CH)b - (R. CH)c - (R1. CH)d - &c. where R is an alkyl group, R1 is an alkyl group or hydrogen, and n, a, b, c, d ... &c. are integers such that n, and the sum of a + b + c + d + ... &c. are each greater than 10 and generally between 50 and 10,000.  Substances which may be reacted are diazoethane and 1-diazopropane, singly or together; diazomethane mixed with diazoethane or 1-diazopropane; higher 1-diazoalkanes, such as 1-diazopentane, 1-diazoheptane and 1-diazooctadecane, mixed with diazomethane, diazoethane or 1-diazopropane.  The reaction is preferably carried out in a solvent, e.g. ether, in anhydrous conditions, at 0-20 DEG C.  The catalyst is added in small quantities until the yellow colour disappears, the solution is filtered and the ether distilled off.  Suitable catalysts are finely divided copper, copper bronze, anhydrous CuSO4, Cu2O, (Cu2(CN)2 and CuCl2.  Polyethylidene and polypropylidene are hard, fusible, inert glasses, amorphous, and soluble in ether and hydrocarbons but not in alcohols. Interpolymers prepared from diazomethane and a higher diazoalkane containing more than 80 per cent. methylene groups are tough, flexible, crystalline solids insoluble in ether and cold hydrocarbons but soluble in hot aromatic hydrocarbons.  Those containing less than 80 per cent. methylene groups tend to the amorphous state.  The products are useful in electrical insulation, for sheet formation and in mouldings.ALSO:Polyalkylidenes or interpolyalkylidenes are prepared by contacting a 1-diazoalkane containing 2 or 3 carbon atoms, or a mixture of a 1-diazoalkane of not more than 3 carbon atoms and a 1-diazoalkane of 2 or more carbon atoms, with copper or a copper-containing substance, and allowing the evolution of nitrogen. The polyalkylidenes, which are glassy, have the formula-(R.CH)n, and the interpolyalkylidenes, which may be glassy or liquid, have the formula -(R.CH)a-(R1.CH)b-(R.CH)c-(R1CH) d-&c., where R is an alkyl group, R1 is an alkyl group or hydrogen, and n, a, b, c, d . . . &c. are integers such that n, and the sum of a + b + c + d + . . &c. are each greater than 10 and generally between 50 and 10,000.  Substances which may be reacted are diazoethane and 1-diazopropane, singly or together; diazomethane mixed with diazoethane or 1-diazopropane; higher 1-diazoalkanes, such as 1-diazopentane, 1-diazoheptane and 1-diazooctadecane, mixed with diazomethane, diazoethane or 1-diazopropane.  The reaction is preferably carried out in a solvent, e.g. ether, in anhydrous conditions, at 0-20 DEG C.  The catalyst is added in small quantities until the yellow colour disappears, the solution is filtered and the ether distilled off. Suitable catalysts are finely divided copper, copper bronze, anhydrous CuSo4, Cu2O, Cu2(CN)2 and CuCl2.  Polyethylidene and polypropylidene are hard, fusible, inert glasses, amorphous, and soluble in ether and hydrocarbons but not in alcohols.  Interpolymers prepared from diazomethane and a higher diazoalkane containing more than 80 per cent. methylene groups are tough, flexible, crystalline solids insoluble in ether and cold hydrocarbons but soluble in hot aromatic hydrocarbons.  Those containing less than 80 per cent. methylene groups tend to the amorphous state.  The products are useful in electrical insulation, for sheet formation and in mouldings.